CN114752337A - Waterproof MS sealant and preparation method thereof - Google Patents
Waterproof MS sealant and preparation method thereof Download PDFInfo
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- CN114752337A CN114752337A CN202210516636.6A CN202210516636A CN114752337A CN 114752337 A CN114752337 A CN 114752337A CN 202210516636 A CN202210516636 A CN 202210516636A CN 114752337 A CN114752337 A CN 114752337A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a waterproof MS sealant and a preparation method thereof, wherein the scheme is that a diepoxy terminated polyether and gamma-aminopropyltrimethoxysilane are subjected to polymerization reaction to generate MS resin, the MS resin is used as base resin, and components such as a plasticizer, nano calcium carbonate, graphene, carbon black, a water removing agent vinyl trimethoxysilane, gamma-aminopropyltrimethoxysilane, a flame retardant, a catalyst and the like are added to prepare the MS sealant; due to the introduction of the graphene, the flame retardant and the gamma-aminopropyltrimethoxysilane, the MS sealant has excellent water resistance, medium resistance and flame retardance, and can be widely applied to various application environments. The components of the MS sealant are appropriate in proportion, the process design is reasonable, the prepared MS sealant is high in crosslinking density, excellent in bonding strength and peeling strength, good in water resistance and excellent in flame retardant property, can be widely applied to multiple fields, and is high in practicability.
Description
Technical Field
The invention relates to the technical field of sealants, in particular to a waterproof MS sealant and a preparation method thereof.
Background
The silane modified polyether (MS) sealant takes polyether polymer as a base material, is mixed with filler and plasticizer, and is polymerized and cured under the action of moisture to achieve the aims of sealing and bonding. The MS sealant does not contain silicone components and solvents, does not contain polyurethane groups, is odorless in most formulas, can be sprayed, has good elasticity, is suitable for bonding among various base materials, can absorb and compensate dynamic load, can slow down material fatigue, and is widely applied to bonding and sealing of parts such as automobiles, trains, ships, track containers, ventilation pipelines and the like.
Nowadays, MS sealant has poor water resistance, and along with wide application, the requirement on flame retardance of the MS sealant is higher and higher, so based on the situation, the application discloses the water-resistant MS sealant and a preparation method thereof, so as to solve the technical scheme.
Disclosure of Invention
The invention aims to provide a waterproof MS sealant and a preparation method thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the waterproof MS sealant comprises the following steps:
(1) taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol, heating to 70-80 ℃ in a nitrogen environment, slowly dropwise adding triethylamine for 20-30 min, reacting for 8-10 h under heat preservation, cooling to-5 ℃, introducing ammonia gas, reacting for 20-24 h, collecting a product, washing with deionized water, and removing a solvent by rotary evaporation to obtain a propargyl-containing flame-retardant monomer;
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 20-30 min, adding a catalyst, reacting at 60-70 ℃ for 20-24 h, evaporating to remove the solvent, and recrystallizing to obtain a flame retardant;
(3) mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 30-40 min, heating to 100-110 ℃, dehydrating for 2-2.5 h, cooling to 40-45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
According to an optimized scheme, in the step (3), the raw materials of the components comprise the following components in percentage by mass: 25-30 wt% of MS resin, 20-22 wt% of plasticizer, 1-2 wt% of vinyl trimethoxy silane, 0.2-0.5 wt% of gamma-aminopropyl trimethoxy silane, 3-6 wt% of flame retardant, 0.1-0.3 wt% of catalyst, 1.5-2 wt% of graphene, 8-10 wt% of carbon black and the balance of nano calcium carbonate.
In the optimized scheme, in the step (1), the preparation steps of the 2- (4-aminophenyl) hexafluoroisopropanol are as follows: heating p-toluenesulfonic acid and aniline to 100-105 ℃, dropwise adding hexafluoroacetone trihydrate under a nitrogen environment for 20-30 min, carrying out heat preservation and reflux reaction for 5-6 h, cooling, dissolving with ethanol, filtering, washing, and collecting a product to obtain 2- (4-aminophenyl) hexafluoroisopropanol.
In an optimized scheme, the molar ratio of the aniline to the hexafluoroacetone trihydrate is 1: 3; the dosage of the p-toluenesulfonic acid is 6-7 wt% of the mass of the aniline.
In an optimized scheme, in the step (1), the preparation steps of the p-aminophenylpropargyl ether are as follows: mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 70-75 ℃ for 7-8 h, adding sodium hydroxide to adjust the pH value to 7, extracting, washing and drying to obtain the p-aminophenylpropargyl ether.
In a more optimized scheme, in the step (1), the molar ratio of the p-aminophenylpropargyl ether to the 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1; the molar ratio of the total molar amount of the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol to the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: (0.4-0.5).
In a more optimized scheme, the plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
In the preferred embodiment, in step (3), the preparation of the MS resin comprises the following steps: taking diepoxy terminated polyether and gamma-aminopropyltrimethoxysilane, stirring for 20-30 min, and reacting for 6-8 h at 40-50 ℃ to obtain MS resin; the mol ratio of the diepoxy terminated polyether to the gamma-aminopropyltrimethoxysilane is 1: 1.3.
according to an optimized scheme, the MS sealant is prepared by the preparation method of the waterproof MS sealant.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a waterproof MS sealant and a preparation method thereof, wherein the scheme is that a diepoxy terminated polyether and gamma-aminopropyltrimethoxysilane are subjected to polymerization reaction to generate MS resin, the MS resin is used as base resin, and components such as a plasticizer, nano calcium carbonate, graphene, carbon black, a water removing agent vinyl trimethoxysilane, gamma-aminopropyltrimethoxysilane, a flame retardant, a catalyst and the like are added to prepare the MS sealant; due to the introduction of the graphene, the flame retardant and the gamma-aminopropyltrimethoxysilane, the MS sealant has excellent water resistance and medium resistance, has excellent flame retardance, and can be widely applied to various application environments.
When the flame retardant is prepared in the scheme, hexachlorocyclotriphosphazene, p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol react in a triethylamine environment, and amino groups in the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol and the hexachlorocyclotriphosphazene undergo nucleophilic substitution, so that a propargyl-containing flame retardant monomer is formed; then ammonia is introduced to carry out ammoniation, so that the flame-retardant monomer contains abundant amino; the existence of the amino can improve the crosslinking density of the sealant, so that the water resistance of the sealant is improved; meanwhile, the addition of the 2- (4-aminophenyl) hexafluoroisopropanol can introduce fluorine element into the monomer, so as to further improve the water resistance and medium resistance of the sealant.
According to the scheme, propargyl is introduced into the flame retardant through p-aminophenyl propargyl ether, and then the propargyl and active hydrogen contained in the double-layer silsesquioxane are utilized to carry out hydrosilylation reaction to prepare the composite flame retardant; due to the existence of double-layer silsesquioxane and hexachlorocyclotriphosphazene, the flame retardant property of the sealant product is improved by utilizing the synergistic effect between phosphorus and silicon.
In the above scheme, the present application defines that "the molar ratio of p-aminophenylpropargyl ether to 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1', because the flame-retardant monomer contains abundant amino and the existence of siloxane, the introduction amount of fluorine element in the scheme does not need to be too much, and the existence of p-aminophenylpropargyl ether ensures the flame-retardant performance of the product, because the molar weight of the fluorine element is more than 2- (4-aminophenyl) hexafluoroisopropanol, and the optimum is 3: 1.
the invention discloses a waterproof MS sealant and a preparation method thereof, the components are appropriate in proportion, the process design is reasonable, the prepared MS sealant is higher in crosslinking density, more excellent in bonding strength and peeling strength, better in water resistance and more excellent in flame retardant property, can be widely applied to multiple fields, and is higher in practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples:
the preparation steps of the MS resin are as follows: taking diepoxy terminated polyether (HY-3000, produced by Jiangsu Stanshan New Material Co., Ltd., molecular weight of 3000, average polymerization degree of 50) and gamma-aminopropyltrimethoxysilane, stirring for 30min, and reacting at 40 ℃ for 7h to obtain MS resin; the mol ratio of the diepoxy terminated polyether to the gamma-aminopropyltrimethoxysilane is 1: 1.3.
example 1:
the preparation method of the waterproof MS sealant comprises the following steps:
(1) heating p-toluenesulfonic acid and aniline to 100 ℃, dropwise adding hexafluoroacetone trihydrate under a nitrogen environment for 30min, carrying out heat preservation and reflux reaction for 6h, cooling, dissolving with ethanol, filtering, washing, and collecting a product to obtain 2- (4-aminophenyl) hexafluoroisopropanol. The molar ratio of aniline to hexafluoroacetone trihydrate is 1: 3; the dosage of the p-toluenesulfonic acid is 6 wt% of the mass of the aniline.
Mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 70 deg.C for 8h, adding sodium hydroxide to adjust pH to 7, extracting, washing, and drying to obtain p-aminophenylpropargyl ether. The dosage of the p-acetamidophenylpropargyl ether and hydrochloric acid is 0.1 mol: 200 mL; the volume ratio of the hydrochloric acid to the ethanol is 1: 1.
taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol, heating to 70 ℃ under a nitrogen environment, slowly dropwise adding triethylamine for 30min, carrying out heat preservation reaction for 10h, cooling to 5 ℃, introducing ammonia gas, reacting for 24h, collecting a product, washing with deionized water, and carrying out rotary evaporation to remove a solvent, thereby obtaining a propargyl-containing flame-retardant monomer; the molar ratio of the p-aminophenylpropargyl ether to the 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1; the molar ratio of the total molar amount of the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol to the molar amount of the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: 0.4.
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 20min, adding a catalyst, reacting for 24h at 60 ℃, evaporating to remove the solvent, and recrystallizing to obtain a flame retardant; the molar ratio of the double-layer silsesquioxane to the propargyl-containing flame-retardant monomer is 1: 1, the dosage of the catalyst and the dosage of the double-layer silsesquioxane are 80 μ L: 2g of the total weight.
(3) Mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 30min, heating to 100 ℃, dehydrating for 2.5h, cooling to 40 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
25 wt% of MS resin, 20 wt% of plasticizer, 1 wt% of vinyl trimethoxy silane, 0.5 wt% of gamma-aminopropyl trimethoxy silane, 6 wt% of flame retardant, 0.3 wt% of catalyst, 1.5 wt% of graphene, 8 wt% of carbon black and the balance of nano calcium carbonate. The plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
Example 2:
the preparation method of the waterproof MS sealant comprises the following steps:
(1) heating p-toluenesulfonic acid and aniline to 105 ℃, dropwise adding hexafluoroacetone trihydrate under a nitrogen environment for 25min, carrying out heat preservation and reflux reaction for 5.5h, cooling, dissolving with ethanol, filtering, washing, and collecting a product to obtain 2- (4-aminophenyl) hexafluoroisopropanol. The molar ratio of aniline to hexafluoroacetone trihydrate is 1: 3; the dosage of the p-toluenesulfonic acid is 6 wt% of the mass of the aniline.
Mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 75 deg.C for 7.5h, adding sodium hydroxide to adjust pH to 7, extracting, washing, and drying to obtain p-aminophenylpropargyl ether. The dosage of the p-acetamidophenylpropargyl ether and hydrochloric acid is 0.1 mol: 200 mL; the volume ratio of the hydrochloric acid to the ethanol is 1: 1.
taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol, heating to 7 ℃ under a nitrogen environment, slowly dropwise adding triethylamine for 2min, keeping the temperature for reaction for 9h, cooling to 5 ℃, introducing ammonia gas, reacting for 22h, collecting a product, washing with deionized water, and removing a solvent by rotary evaporation to obtain a propargyl-containing flame-retardant monomer; the molar ratio of the p-aminophenylpropargyl ether to the 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1; the molar ratio of the total molar amount of the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol to the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: 0.4.
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 25min, adding a catalyst, reacting for 22h at 65 ℃, evaporating to remove a solvent, and recrystallizing to obtain a flame retardant; the double-layer silsesquioxane and the propargyl-containing flame-retardant monomer are prepared from the following components in a molar ratio of 1: 1, the dosage of the catalyst and the dosage of the double-layer silsesquioxane are 80 mu L: 2g of the total weight of the composition.
(3) Mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 35min, heating to 105 ℃, dehydrating for 2.5h, cooling to 45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
30 wt% of MS resin, 21 wt% of plasticizer, 2 wt% of vinyl trimethoxy silane, 0.5 wt% of gamma-aminopropyl trimethoxy silane, 6 wt% of flame retardant, 0.2 wt% of catalyst, 1.5 wt% of graphene, 9 wt% of carbon black and the balance of nano calcium carbonate. The plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
Example 3:
the preparation method of the waterproof MS sealant comprises the following steps:
(1) heating p-toluenesulfonic acid and aniline to 105 ℃, dropwise adding hexafluoroacetone trihydrate under a nitrogen environment for 20min, carrying out heat preservation and reflux reaction for 5h, cooling, dissolving with ethanol, filtering, washing, and collecting a product to obtain 2- (4-aminophenyl) hexafluoroisopropanol. The molar ratio of aniline to hexafluoroacetone trihydrate is 1: 3; the dosage of the p-toluenesulfonic acid is 6 wt% of the mass of the aniline.
Mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 75 deg.C for 7h, adding sodium hydroxide to adjust pH to 7, extracting, washing, and drying to obtain p-aminophenylpropargyl ether. The dosage of the p-acetamidophenylpropargyl ether and hydrochloric acid is 0.1 mol: 200 mL; the volume ratio of the hydrochloric acid to the ethanol is 1: 1.
taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol, heating to 80 ℃ in a nitrogen environment, slowly dropwise adding triethylamine for 30min, reacting for 8h under heat preservation, cooling to 5 ℃, introducing ammonia gas, reacting for 24h, collecting a product, washing with deionized water, and removing a solvent by rotary evaporation to obtain a flame-retardant monomer containing propargyl; the molar ratio of the p-aminophenylpropargyl ether to the 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1; the molar ratio of the total molar amount of the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol to the molar amount of the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: 0.4.
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 30min, adding a catalyst, reacting for 20h at 70 ℃, evaporating to remove a solvent, and recrystallizing to obtain a flame retardant; the double-layer silsesquioxane and the propargyl-containing flame-retardant monomer are prepared from the following components in a molar ratio of 1: 1, the dosage of the catalyst and the dosage of the double-layer silsesquioxane are 80 μ L: 2g of the total weight.
(3) Mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 40min, heating to 110 ℃, dehydrating for 2h, cooling to 45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
30 wt% of MS resin, 22 wt% of plasticizer, 2 wt% of vinyl trimethoxy silane, 0.5 wt% of gamma-aminopropyl trimethoxy silane, 6 wt% of flame retardant, 0.3 wt% of catalyst, 1.5 wt% of graphene, 10 wt% of carbon black and the balance of nano calcium carbonate. The plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
Comparative example 1: comparative example 1 a control was carried out on the basis of example 2, in comparative example 1 no graphene was added and the remaining process and components were unchanged.
The preparation method of the waterproof MS sealant comprises the following steps:
(1) heating p-toluenesulfonic acid and aniline to 105 ℃, dropwise adding hexafluoroacetone trihydrate under a nitrogen environment for 25min, carrying out heat preservation and reflux reaction for 5.5h, cooling, dissolving with ethanol, filtering, washing, and collecting a product to obtain 2- (4-aminophenyl) hexafluoroisopropanol. The molar ratio of aniline to hexafluoroacetone trihydrate is 1: 3; the dosage of the p-toluenesulfonic acid is 6 wt% of the mass of the aniline.
Mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 75 deg.C for 7.5h, adding sodium hydroxide to adjust pH to 7, extracting, washing, and drying to obtain p-aminophenylpropargyl ether. The dosage of the p-acetamidophenylpropargyl ether and hydrochloric acid is 0.1 mol: 200 mL; the volume ratio of the hydrochloric acid to the ethanol is 1: 1.
taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol, heating to 7 ℃ under a nitrogen environment, slowly dropwise adding triethylamine for 2min, keeping the temperature for reaction for 9h, cooling to 5 ℃, introducing ammonia gas, reacting for 22h, collecting a product, washing with deionized water, and removing a solvent by rotary evaporation to obtain a propargyl-containing flame-retardant monomer; the molar ratio of the p-aminophenylpropargyl ether to the 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1; the molar ratio of the total molar amount of the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol to the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: 0.4.
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 25min, adding a catalyst, reacting for 22h at 65 ℃, evaporating to remove a solvent, and recrystallizing to obtain a flame retardant; the double-layer silsesquioxane and the propargyl-containing flame-retardant monomer are prepared from the following components in a molar ratio of 1: 1, the dosage of the catalyst and the dosage of the double-layer silsesquioxane are 80 mu L: 2g of the total weight of the composition.
(3) Mixing MS resin, a plasticizer, nano calcium carbonate and carbon black, stirring for 35min, heating to 105 ℃, dehydrating for 2.5h, cooling to 45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
30 wt% of MS resin, 21 wt% of plasticizer, 2 wt% of vinyl trimethoxy silane, 0.5 wt% of gamma-aminopropyl trimethoxy silane, 6 wt% of flame retardant, 0.2 wt% of catalyst, 9 wt% of carbon black and the balance of nano calcium carbonate. The plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
Comparative example 2: comparative example 2 a control was performed on the basis of example 2, and in comparative example 2, the kinds of flame retardants were adjusted, the flame retardants were aluminum hydroxide and magnesium hydroxide, and the remaining processes and components were unchanged.
The preparation method of the waterproof MS sealant comprises the following steps:
(1) mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 35min, heating to 105 ℃, dehydrating for 2.5h, cooling to 45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
30 wt% of MS resin, 21 wt% of plasticizer, 2 wt% of vinyl trimethoxy silane, 0.5 wt% of gamma-aminopropyl trimethoxy silane, 6 wt% of flame retardant, 0.2 wt% of catalyst, 1.5 wt% of graphene, 9 wt% of carbon black and the balance of nano calcium carbonate. The plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate; the flame retardant is prepared from aluminum hydroxide and magnesium hydroxide in a mass ratio of 1: 1 and mixing.
Comparative example 3: comparative example 3 a control was made on the basis of example 2, in comparative example 3 no 2- (4-aminophenyl) hexafluoroisopropanol was introduced, and the remaining process and components were unchanged.
The preparation method of the waterproof MS sealant comprises the following steps:
(1) mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 75 deg.C for 7.5h, adding sodium hydroxide to adjust pH to 7, extracting, washing, and drying to obtain p-aminophenylpropargyl ether. The dosage of the p-acetamidophenylpropargyl ether and hydrochloric acid is 0.1 mol: 200 mL; the volume ratio of the hydrochloric acid to the ethanol is 1: 1.
taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether, heating to 7 ℃ in a nitrogen environment, slowly dropwise adding triethylamine for 2min, carrying out heat preservation reaction for 9h, cooling to 5 ℃, introducing ammonia gas, reacting for 22h, collecting a product, washing with deionized water, and removing a solvent by rotary evaporation to obtain a propargyl-containing flame-retardant monomer; the molar ratio of the p-aminophenylpropargyl ether to the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: 0.4.
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 25min, adding a catalyst, reacting for 22h at 65 ℃, evaporating to remove a solvent, and recrystallizing to obtain a flame retardant; the double-layer silsesquioxane and the propargyl-containing flame-retardant monomer are prepared from the following components in a molar ratio of 1: 1, the dosage of the catalyst and the dosage of the double-layer silsesquioxane are 80 μ L: 2g of the total weight of the composition.
(3) Mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 35min, heating to 105 ℃, dehydrating for 2.5h, cooling to 45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
30 wt% of MS resin, 21 wt% of plasticizer, 2 wt% of vinyl trimethoxy silane, 0.5 wt% of gamma-aminopropyl trimethoxy silane, 6 wt% of flame retardant, 0.2 wt% of catalyst, 1.5 wt% of graphene, 9 wt% of carbon black and the balance of nano calcium carbonate. The plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
Comparative example 4: comparative example 4 a control was carried out on the basis of example 2, in comparative example 4 no ammonia gas was fed in and the remaining process and components were unchanged.
The preparation method of the waterproof MS sealant comprises the following steps:
(1) heating p-toluenesulfonic acid and aniline to 105 ℃, dropwise adding hexafluoroacetone trihydrate under a nitrogen environment for 25min, carrying out heat preservation and reflux reaction for 5.5h, cooling, dissolving with ethanol, filtering, washing, and collecting a product to obtain 2- (4-aminophenyl) hexafluoroisopropanol. The molar ratio of aniline to hexafluoroacetone trihydrate is 1: 3; the dosage of the p-toluenesulfonic acid is 6 wt% of the mass of the aniline.
Mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 75 deg.C for 7.5h, adding sodium hydroxide to adjust pH to 7, extracting, washing, and drying to obtain p-aminophenylpropargyl ether. The dosage of the p-acetamidophenylpropargyl ether and hydrochloric acid is 0.1 mol: 200 mL; the volume ratio of the hydrochloric acid to the ethanol is 1: 1.
taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol, heating to 7 ℃ under a nitrogen environment, slowly dropwise adding triethylamine for 2min, reacting for 9h under heat preservation, collecting a product, washing with deionized water, and removing the solvent by rotary evaporation to obtain a propargyl-containing flame-retardant monomer; the molar ratio of the p-aminophenylpropargyl ether to the 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1; the molar ratio of the total molar amount of the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol to the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: 0.4.
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 25min, adding a catalyst, reacting for 22h at 65 ℃, evaporating to remove a solvent, and recrystallizing to obtain a flame retardant; the molar ratio of the double-layer silsesquioxane to the propargyl-containing flame-retardant monomer is 1: 1, the dosage of the catalyst and the dosage of the double-layer silsesquioxane are 80 μ L: 2g of the total weight.
(3) Mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 35min, heating to 105 ℃, dehydrating for 2.5h, cooling to 45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
30 wt% of MS resin, 21 wt% of plasticizer, 2 wt% of vinyl trimethoxy silane, 0.5 wt% of gamma-aminopropyl trimethoxy silane, 6 wt% of flame retardant, 0.2 wt% of catalyst, 1.5 wt% of graphene, 9 wt% of carbon black and the balance of nano calcium carbonate. The plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
Detection experiment:
taking the sealants prepared in the examples 1-3 and the comparative examples 1-4, preparing a sheet in a polytetrafluoroethylene mold, and vulcanizing the sheet for 7 days at the temperature of 25 ℃ and the humidity of 50% to obtain a test sample;
1. according to the GB/T13477-1992 'test method for building sealing materials', a universal electronic tensile tester is adopted to test the tensile strength.
2. Immersion test: the test was carried out according to test method A, appendix of the standard JC/T881-2001 "sealants for concrete building joints".
3. Respectively placing the sample in pure water, a sodium hydroxide solution with the pH value of 11 and a hydrochloric acid solution with the pH value of 3, soaking for 7 days, and then detecting the tensile strength of the sample again.
And (4) conclusion: the invention discloses a waterproof MS sealant and a preparation method thereof, the components are appropriate in proportion, the process design is reasonable, the prepared MS sealant is higher in crosslinking density, more excellent in bonding strength and peeling strength, better in water resistance and more excellent in flame retardant property, can be widely applied to multiple fields, and is higher in practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the waterproof MS sealant is characterized by comprising the following steps: the method comprises the following steps:
(1) taking hexachlorocyclotriphosphazene and toluene, mixing and stirring until the hexachlorocyclotriphosphazene and the toluene are dissolved, adding p-aminophenylpropargyl ether and 2- (4-aminophenyl) hexafluoroisopropanol, heating to 70-80 ℃ in a nitrogen environment, slowly dropwise adding triethylamine for 20-30 min, reacting for 8-10 h under heat preservation, cooling to-5 ℃, introducing ammonia gas, reacting for 20-24 h, collecting a product, washing with deionized water, and removing a solvent by rotary evaporation to obtain a propargyl-containing flame-retardant monomer;
(2) mixing double-layer silsesquioxane and a flame-retardant monomer containing propargyl, adding anhydrous tetrahydrofuran in a nitrogen environment, stirring for 20-30 min, adding a catalyst, reacting at 60-70 ℃ for 20-24 h, evaporating to remove the solvent, and recrystallizing to obtain a flame retardant;
(3) mixing MS resin, a plasticizer, nano calcium carbonate, graphene and carbon black, stirring for 30-40 min, heating to 100-110 ℃, dehydrating for 2-2.5 h, cooling to 40-45 ℃, adding vinyl trimethoxy silane, gamma-aminopropyl trimethoxy silane, a flame retardant and a catalyst in a nitrogen environment, uniformly mixing, and defoaming to obtain a finished product.
2. The method for preparing a water-resistant MS sealant as claimed in claim 1, characterized in that: in the step (3), the raw materials of the components comprise the following components in percentage by mass: 25-30 wt% of MS resin, 20-22 wt% of plasticizer, 1-2 wt% of vinyl trimethoxy silane, 0.2-0.5 wt% of gamma-aminopropyl trimethoxy silane, 3-6 wt% of flame retardant, 0.1-0.3 wt% of catalyst, 1.5-2 wt% of graphene, 8-10 wt% of carbon black and the balance of nano calcium carbonate.
3. The method for preparing a water-resistant MS sealant as claimed in claim 1, characterized in that: in the step (1), the preparation of the 2- (4-aminophenyl) hexafluoroisopropanol comprises the following steps: heating p-toluenesulfonic acid and aniline to 100-105 ℃, dropwise adding hexafluoroacetone trihydrate under a nitrogen environment for 20-30 min, carrying out heat preservation and reflux reaction for 5-6 h, cooling, dissolving with ethanol, filtering, washing, and collecting a product to obtain 2- (4-aminophenyl) hexafluoroisopropanol.
4. The method for preparing a water-resistant MS sealant according to claim 3, which is characterized in that: the molar ratio of aniline to hexafluoroacetone trihydrate is 1: 3; the dosage of the p-toluenesulfonic acid is 6-7 wt% of the mass of the aniline.
5. The method for preparing a water-resistant MS sealant as claimed in claim 1, characterized in that: in the step (1), the preparation of the p-aminophenyl propargyl ether comprises the following steps: mixing p-acetamidophenylpropargyl ether and ethanol, adding hydrochloric acid, stirring at 70-75 ℃ for 7-8 h, adding sodium hydroxide to adjust the pH value to 7, extracting, washing and drying to obtain the p-aminophenylpropargyl ether.
6. The method for preparing a water-resistant MS sealant according to claim 1, which is characterized in that: in the step (1), the molar ratio of the p-aminophenylpropargyl ether to the 2- (4-aminophenyl) hexafluoroisopropanol is 3: 1; the molar ratio of the total molar amount of the p-aminophenylpropargyl ether and the 2- (4-aminophenyl) hexafluoroisopropanol to the hexachlorocyclotriphosphazene is 3: 1, the mass ratio of hexachlorocyclotriphosphazene to triethylamine is 1: (0.4-0.5).
7. The method for preparing a water-resistant MS sealant according to claim 1, which is characterized in that: the plasticizer is diisononyl phthalate; the catalyst is dibutyltin dilaurate.
8. The method for preparing a water-resistant MS sealant according to claim 1, which is characterized in that: in the step (3), the preparation of the MS resin comprises the following steps: taking diepoxy terminated polyether and gamma-aminopropyltrimethoxysilane, stirring for 20-30 min, and reacting for 6-8 h at 40-50 ℃ to obtain MS resin; the mol ratio of the diepoxy terminated polyether to the gamma-aminopropyltrimethoxysilane is 1: 1.3.
9. the MS sealant prepared by the preparation method of the water-resistant MS sealant according to any one of claims 1 to 8.
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| CN116694285A (en) * | 2023-08-07 | 2023-09-05 | 信泰永合(烟台)新材料有限公司 | High-modulus flame-retardant MS adhesive and preparation method thereof |
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